Vat dyestuffs of the di-thionaphthenylene-quinone series and a process of preparing them



Patented June 20, 1933 UNITED STATES PATENT OFFI FRITZ MAYER, OF FRANKFORT-ON-THE-MAIN, GERMANY, ASSIGNOB TO GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., A CORPORATION OF DELAWAR-E VAT DYESTUFFS OF THE DI-TI-IIONAPHTHENYLENE-QUINONE SERIES AND A PROCESS OF PREPARING THEM No Drawing. Application filed June 11, 1929, Serial No. 370,164, and in Germany June 29, 1928.

The present invention relates to vat dyestuffs of the di-thionaphthenylene-quinone series and to a process of preparing them.

I have found that valuable vat dyestuffs are obtainable by treating the derivatives of 2.2-di-thionaphthenyl-ketone of the following formula:

COOH

l OOOH wherein the benzene nuclei may be substituted or not by any univalent residue, with agents capable of splitting off water and then heating the product thus obtained alone or with the addition of aluminium chloride, if necessary, in the presence of a melting agent.

Thus for instance there is obtained from 2 2-di-thionaphthenyl-lretone-3.3-dicarboxylic acid of the following formula:

OOH

COOH

by splitting off successively 1 mol. of Water and 1 mol. of carbon dioxide the di-thlonaphthenylene-quinone of the formula:

dyeing WOOl fast golden-yellow tints. During the course of the above reaction there is formed as intermediate product an anhydroproduct which has probably one of the following formulae:

CG GO @1 From such an anhydro-product the carbon dioxide may for instance be split off by wherein the benzene nuclei may be substituted or not by any univalent residue. These '5 dyestuffs are yellow to brown products which are soluble in concentrated sulfuric acid to a blue solution and dye wool from a yellow to orange alkaline hydrosulfite vat yellow to orange tints.

The same products are obtainable by using as starting material a di-thionaphthenyl-ketone-mono-carboxylic acid of the following general formula:

coon

wherein the benzene nuclei may be substituted or not by any univalent residue. In this case the reaction is preferably conducted by first converting the mono-carboxylic acid into its chloride and then efiecting the closure of the ring by means of aluminium chloride. One may also arrive at the same result without previously causing formation of the acid chloride.

The following examples serve to illustrate my invention but they are not intended to limit it thereto, the parts being by weight unless otherwise stated.

(1) 30 parts of 2.2-di-thionaphthenylketone-3.3-dicarboxylic acid of the following formula coon COOH

CO CO lowing formula: 0

| J /O Y s \g/ s is revatted. It may be recrystallized from nitrobenzene and melts at 295 C. The product dissolves in sulfuric acid to a pure blue solution and dyes wool from a yellow vat golden-yellow tints.

(2) 12 parts of 2.2-di-thionaphthenylketone-3-carboxylic acid of the following formula:

I melting at between 268 C. and 269 C. and

being prepared by condensing 1 mol. of ortho mercapto-benzaldehyde with 1 mol. of 2-11)- bromo-aceto-thionaphthene-3-carboxylic acid of the formula:

coon

s oo-ore.iar

1 mol. of water and 1 mol. of hydrogen bromide being split off, are transformed into the acid chloride by means of thionylchloride. The acid chloride is dissolved in carbon disulfide, 15 parts of aluminium chloride are added to the solution and the mass is first al lowed to stand and then heated on the water bath for some time. The mixture is then decomposed by the addition of water and hydrochloric acid, the carbon disulfide is blown off by means of steam and the residue is revatted. By this operation a dithionaphthenylene-quinone is obtained which is identical with that described in Example 1.

(3) 15 parts of 4.4-dimethyl-6.6-dichloro- 2.2-di-thionaphthianyl-ketone3.3-dicarboxylic acid of the following formula:

0,113 COOH OOOH CH melting above 340 C. and being prepared by treating 2 mol. of l-methyl-G-chloro-thionaphthene-quinone of the melting point of from 129 C. to 130 C. with 1 mol. of symmetrical dichloroacetone, 2 mol. of hydrogen chloride and 2 mol. of water being split off, are boiled for minutes with parts by volume of acetic anhydride. The acid is transformed into the anhydro-product without being previously dissolved. It also melts above 340 C. 10 parts of the so formed anhydro-product are gradually introduced at 175 G. into a melt of 10 parts of aluminium chloride and 10 parts of sodium chloride, the temperature being maintained at this stage until the formation of the dyestufi' is complete. Thereupon the melt is decomposed with water and-the residue is revatted. The resulting 4.4-dimethyl-0.6-dichloro-di-thionaphthenylene-quinone of the following formula:

CH3 CH3 forms, when recrystallized from nitrobenzene, red needles of the melting point of 332 C. The dyestuif forms an orange vat and dissolves in concentrated sulfuric acid to a reddish-blue solution.

(4;) 10.6 parts of 4-methyl-6-chloro-thionaphthene-quinone of the following formula:

are dissolved in 100 parts by volume of a solution of sodium carbonate of 10 per cent strength, 5 parts of monochloracetone are added and the solution is boiled for minutes. After cooling, the resulting sodium salt of 2-acetyl--methyl-G-chloro-thionaphthene-3-carboxylic acid is filtered by suction and decomposed by means of hydrochloric acid. The acid itself melts at between 179 and 180 C. and has the following formula:

( 3m COOH 01 S/\(|3/OH:;

10 parts of this acid are dissolved in parts by volume of glacial acetic acid and mixed with 7.4 parts of bromine. The mass is heated on the water bath and, after cooling, the resulting o-bromo-derivative of the formula:

CH2 COOH melting at between 217 C. and 218 C. is filtered by suction. 10 parts of the said acid are dissolved in 100 parts by volume of methanol and added to a solution of 4.7 parts of thionaphthene-quinone in parts by volume of caustic soda solution of 10 per cent strength. The solution freed from the methanol is precipitated by means of hydrochloric acid and the resulting 4-methyl-6- chloro-di-thionaphthenylene-3.3-dicarboxylic acid is recrystallized from introbenzene. It melts at 287 C. and has the following formula:

CH: OOOH OOOH 7 parts of this acid are boiled for 15 minutes with 35 parts of acetic anhydride. After cooling, the anhydro-product melting at between i-Bl" C. and 315 C. is filtered by suction. 10 parts of the anhydro-product are gradually introduced at 140 G. into a melt 0 I (K C]/ V I claim: 1. The process which comprises treating a compound of the following formula:

OOOH COOH wherein the benzene nuclei may contain substituents selected from the group consisting of chlorine atoms and methyl groups with an organic carboxylic acid anhydride capable of splitting off water and then heating the intermediate product thus obtained.

2. The process which comprises treating a compound of the following formula:

COOH OOOH wherein the benzene nuclei may contain substituents selected from the group consisting of chlorine atoms and methyl groups with acetic anhydride and then heating the intermediate product thus obtained.

3. The process which comprises treating a compound of the following formula:

[00H coon s 3 s 0 wherein the benzene nuclei may contain substituents selected from the group consisting of chlorine atoms and methyl groups with acetic anhydride and then heating the intermediate product thus obtained with aluminium chloride in the presence of a flux.

4. The process which comprises treating a compound of the followmg formula:

OOOH COOH \s/k ls/ 2 wherein the benzene nuclei may contain substituents selected from the group consisting of chlorine atoms and methyl groups with acetic anhydride and then heating the intermediate product thus obtained with sodium-aluminium chloride.

5. The process which comprises treating a compound of the following formula:

III COOH COOH X ka /O\Y t wherein X stands for hydrogen or methyl, Y for hydrogen or chlorine, with an organic carboxylic acid anhydride capable of splitting off water and then heating the intermediate product thus obtained. 1

(5. T he process which comprises treating a ompound of the following formula:

X 00011 COOH X Y s s Y H wherein X stands for hydrogen or methyl, Y for hydrogen or chlorine, with acetic anhydride and then heating the intermediate product thus obtained.

7. The process which comprises treating a compound of the following probable formula:

product thus obtained with sodium-aluminium chloride.

8. The process which comprises treating a compound of the following formula:

OOH

X C 00011 Y O S C S O wherein X stands for hydrogen or methyl and Y for hydrogen or chlorine, with an organic carboxylic acid anhydride capable of splitting off water and then heating the intermediate product thus obtained.

9. The process which comprises treating a compound of the following formula:

X COOH OOOH lt t wherein X stands for hydrogen or methyl and Y for hydrogen or chlorine, with acetic anhydride and then heating the intermediate product thus obtained.

10. The process which comprises treating a compound of the following formula:

X C0011 C0011 wherein X stands for hydrogen or methyl and Y for hydrogen or chlorine, with acetic anhydride and then heating the intermediate product thus obtained with sodiumaluminium chloride.

11. The process which comprises treating a compound of the following formula:

COOH COOH with an organic carboxylic acid anhydride capable of splitting off water and then heating the intermediate product thus obtained.

12. The process which comprises treating a compound of the following formula:

COOH COOH with acetic anhydride and then heating the intermediate product thus obtained.

II o 13. The process which comprises treating a compound of the following formula:

(10011 [00011 s s l l with acetic anhydride and then heating the intermediate product thus obtained with sodium-aluminium chloride.

14:. As new products, compounds of the following formula:

15. As new products, compounds of the following formula:

wherein X stands for hydrogen or methyl and Y for hydrogen or chlorine, being yellow to brown products which are soluble in concentrated sulfuric acid to a blue solution and dye wool from a yellow to orange alkaline hydrosulfite vat yellow to orange tints.

16. As new products, compounds of the following formula:

wherein X stands for hydrogen or methyl and Y for hydrogen or chlorine, being yellow to brown products which are soluble in concentrated sulfuric acid to a blue solution and dye wool from a yellow to orange alkaline hydrosulfite vat yellow to orange tints.

17. As a new product, di-thionaphthenylene-quinone of the following formula:

forming an orange powder, being insoluble in water, soluble in higher boiling organic solvents, in sulfuric acid to a blue solution melting at about 295 C. and yielding with alkaline hydrosulfite a yellow vat from which wool is dyed golden-yellow tints.

18. As a new product 4.l--dimethyl-6.6- dichloro-di-thionaphthenylene-quinone of the following formula:

CH: 0 CH3 forming when recrystallized from nitrobenzene, red needles of the melting point of 332 0., dissolving in concentrated sulfuric acid to a reddish blue solution and yielding an orange vat.

19. As a new product l-methyLG-chlorodi-thionaphthenylene-quinone of the following formula:

on o a u Cl/(I; Z0

forming when recrystallized from nitrobenzene, red needles of the melting point of 288 to 289 (1., dissolving in concentrated sulfuric acid to a reddish blue solution and yielding a yellow vat.

In testimony whereof I aflix my signature.

FRITZ MAYER. 

